WO2013167752A1 - Compositions libérant un composé peroxygéné et leur procédé de production - Google Patents

Compositions libérant un composé peroxygéné et leur procédé de production Download PDF

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Publication number
WO2013167752A1
WO2013167752A1 PCT/EP2013/059824 EP2013059824W WO2013167752A1 WO 2013167752 A1 WO2013167752 A1 WO 2013167752A1 EP 2013059824 W EP2013059824 W EP 2013059824W WO 2013167752 A1 WO2013167752 A1 WO 2013167752A1
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Prior art keywords
composition
hydrogen peroxide
μιη
calcium sulfate
dispersion
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PCT/EP2013/059824
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English (en)
Inventor
Frédéric Lakaye
Wim De Windt
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Creachem Sa
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Application filed by Creachem Sa filed Critical Creachem Sa
Priority to IN9212DEN2014 priority Critical patent/IN2014DN09212A/en
Priority to EP13722417.6A priority patent/EP2847128A1/fr
Priority to CN201380024576.5A priority patent/CN104364190A/zh
Priority to US14/399,842 priority patent/US20150086647A1/en
Priority to BR112014028049A priority patent/BR112014028049A2/pt
Priority to RU2014150001A priority patent/RU2014150001A/ru
Publication of WO2013167752A1 publication Critical patent/WO2013167752A1/fr

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
    • C01B15/01—Hydrogen peroxide
    • C01B15/037—Stabilisation by additives
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/46—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/122—Sulfur-containing, e.g. sulfates, sulfites or gypsum
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3937—Stabilising agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/10—Salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • D06L4/12—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • D06L4/13—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability

Definitions

  • the present invention relates to the fields of disinfection, cleaning, personal care, pharmaceutical, textile bleaching and industrial applications.
  • Hydrogen peroxide is a universally useful and environmental friendly oxidizer, sanitizer and disinfection agent. It is a liquid, making it convenient for a large number of bleaching
  • Liquid hydrogen peroxide is an important component of many cleaning, disinfection and sanitizing formulations in sectors SUCH AS food processing, industry/institutional cleaning, consumer goods, medical and health care, and in the agricultural sector. Often, the active component hydrogen peroxide is combined with an alcohol, foaming agents, thickening agents, fragrances, emulsifiers, surfactants, and /or ammonia salts in the final application.
  • Dissociated hydrogen peroxide is relatively stable, and for this reason most commercial products are adjusted to an acid pH. Dissociated hydrogen peroxide breaks down into oxygen and water over a fairly short period of time, and leaves no residue. As a sanitizer it is typically used at concentrations of 0.015 - 0.5 %. At 2-3 % it is classified as a disinfectant.
  • Hydrogen peroxide is also the active component of many bleaching applications in the field of detergents, laundry, paper & pulp.
  • hydrogen peroxide is the most common bleaching agent for protein fibers such as wool and silk, and it is also used extensively for bleaching cellulosic fibers such as cotton.
  • Hydrogen peroxide bleaching is performed in alkaline solution where part of the hydrogen peroxide is converted to the perhydroxy anion (Equation 1).
  • the perhydroxy anion H0 2 ⁇ is generally believed to be the active bleaching species and its concentration in solution increases with hydrogen peroxide concentration, alkalinity and temperature.
  • the alkaline agents most commonly used to generate H0 2 " are caustic soda, carbonates, silicates, pyrophosphates and polyphosphates.
  • Stabilizers are usually added in bleaching products to avoid uncontrolled decomposition reactions of hydrogen peroxide (polyaminocarboxylates, stannates, silicates, etc.).
  • Persalts are salts that release a peracid or peroxy component in the solute water. Persalts and formulations thereof are used as components in a broad range of applications, especially in bleaching.
  • the most commonly used and best known persalts for bleaching formulations are sodium percarbonate and sodium perborate (mono- and tetra hydrate).
  • PMS peroxymonosulfuric acid
  • Another solid oxygen bleach is peroxymonosulfuric acid (PMS), the peroxygen reaction product of hydrogen peroxide and sulfuric acid.
  • PMS is a powerful oxidizing agent, the commercially available salt of which (potassium peroxymonosulfate) is a white solid having a satisfactory shelf life and an active oxygen content of about 4.4%.
  • Perborate is cited as a non- environmentally- sustainable source of peroxide. Boron is ubiquitous in the environment, but substantial deposits of borates are relatively rare. Some studies have implicated boron compounds in causing developmental defects and effects on fertility. Possible effects of sodium perborate are assumed to be due to the degradation product boric acid. Moreover, perborate compounds, mainly used in bleaching applications, and to a minor extent in disinfection, are known to be less effective in the lower temperature ranges (requiring an activator) because of decomposition mainly at elevated temperatures. Percarbonate on the other hand, is more active at lower temperatures compared to perborate.
  • Sodium percarbonate is an attractive persalt for use in detergent compositions: when dissolved in water, sodium percarbonate can eventually release sodium carbonate and hydrogen peroxide. Sodium percarbonate is weight efficient and, after giving up its available oxygen, provides a useful source of carbonate ions for detergency purposes. Hydrogen peroxide and sodium carbonate are known to be environmentally safe, and do not harm textiles when bleaching.
  • the conventional washing powders generally contain sodium percarbonate along with zeolite, a detergent builder, which accelerates the decomposition of sodium percarbonate. Therefore, it is common practice to coat the surface of sodium percarbonate grains with borate, silicate, sulfate or carbonate when it is used together with zeolite, in order to increase stability. Still, sodium percarbonate is generally described as having relatively low stability in detergent formulations. Therefore, many specific processes have been developed to further improve its stability and shelf-life.
  • Dissolving speed in the low temperature range plays a crucial role in effective utilization of sodium percarbonate, especially in cleaning and disinfection of hard surfaces, including textiles.
  • Traditional chemicals used to increase the dissolution rate, such as phosphorus-containing agents, are no longer accepted from an environmental point of view.
  • peroxygen release compositions which must be stable in dry form and in liquid form, with decomposition reactions during shelf life reduced to a very limited extent, and being compatible with other sensitive ingredients in such formulations such as bleach or laundry formulations, cleaning products or sanitizing and disinfection compositions.
  • These peroxygen release compositions must rapidly produce hydrogen peroxide in water at low temperatures. In a dry form, these peroxygen release compositions must have a density and granulate size which is compatible with other ingredients in powder formulations.
  • the peroxygen release composition preferably exhibits a certain viscosity compatible with commercial liquid bleach formulations and sanitizing formulations suitable for foam spraying or other methods of application.
  • thickened hydrogen peroxide releasing compositions that are more stable over time, especially in the presence of catalytically active substances such as metal ions.
  • Environmental considerations further require a reduced presence or total absence of phosphates, and also borate is becoming more and more an undesirable component.
  • both in liquid and dry peroxygen compositions for use in cleaning and disinfection applications there is a need for environmentally acceptable compositions that show enhanced stabilitty, and an enhanced hydrogen peroxide release rate in water in the low temperature range.
  • the present invention relates to a stable viscous peroxygen release composition, containing a non- polymeric thickening agent, not containing environmentally-burdening phosphorus, borate or perborate, and characterized by an enhanced stability in the presence of metal ions.
  • the peroxygen release composition may further be dried into a powder, granular composition or a dried composition with any shape or volume.
  • Dissolution rate plays a crucial role in effective utilization of sodium percarbonate. Although the solubility of sodium percarbonate is inherently good, it is also frequently decreased, for example, by the presence of other salts, which inevitably result from the manufacturing process, such as sodium carbonate (Doetsch W. et al, US 6,248,707). Certain solubilizing agents were included in the past in the persalt formulation, such as alkali metal phosphates, particularly sodium dihydrogen phosphate, or phosphoric acid in liquid formulations, which increased the solubility of the perborate or the percarbonate. Phosphates played also a number of other roles. Today P-free detergents are demanded and phosphate is no longer accepted or only in very limited amounts, for ecological reasons. It is since long reported that large producers, e.g. in Belgium, have now shifted to P-free detergent especially since the production of tablets and liquid detergents (DETIC, press comm. 2001). Different chemicals are today required to achieve comparable performance at an affordable price.
  • the bulk density attainable or the particle size of sodium percarbonate generally can be varied only slightly by the manufacturing methods of the state of the art and is mostly limited from the very start to a narrow range by the type of method or by the sodium carbonate used.
  • the bulk density and particle sizes also need to be controlled, for example for uses in light powder detergents with a low bulk density or in compact detergents with a high bulk density of the detergent, bleach and cleaning agent components. It is also necessary to essentially match the bulk densities of the individual components to each another, in order to largely preclude segregation.
  • Liquid laundry products such as liquid detergents and liquid bleach formulations have become increasingly popular in the last few years.
  • a peroxy bleach system such as is found in powdered detergents based on sodium percarbonate or perborate exhibits poor storage stability in aqueous liquid detergent formulations.
  • a number of prior art studies has focused on stabilizing aqueous persalt solutions with stabilizing agents (e.g. Woods W.G., US 5,380,456). The present invention seeks to overcome this stability issue.
  • stabilizers For thickened liquid hydrogen peroxide compositions suitable for use in a variety of disinfectant, cleaning, personal care, pharmaceutical, textile and industrial applications, stabilizers have also been developed to improve the stability of the thickened composition. Stabilizers are discussed, for example in US Patent numbers 5,997,764 and 6,083,422. Wang identifies an improvement by adding, next to a polymeric thickening agent, also a 3 -component stabilizer system, including phosphorous-containing stabilizers in US 7,045,493. Polymeric organic substances are inherently unstable in contact with hydrogen peroxide, since the latter is an oxidant and may oxidize organic molecules. Presence of metallic ions or organic impurities further catalyze hydrogen peroxide decomposition.
  • this invention relates to a new peroxygen release composition that may contain between 0.5 w % and up to 50 w % of hydrogen peroxide.
  • Such a stable dispersion cannot be obtained when preformed calcium sulfate is added to a hydrogen peroxide solution: the particles of calcium sulfate are de novo synthesized into the hydrogen peroxide solution.
  • the dispersion may then be further dried into a stable, white powder.
  • the viscous dispersion according to this invention is stable without any additional stabilizing agent for hydrogen peroxide, during several months at room temperature. This is surprising, given that most known hydrogen peroxide formulations are unstable unless stabilized by additional stabilizing agents. Without being bound by theory, this advantageous effect may be related to the removal of metal ions by precipitation onto the calcium sulfate fiber, needle or sheet shaped crystals, thereby effectively inactivating the metal ions and preventing catalytic hydrogen peroxide decomposition.
  • the peroxygen release compositions above may be associated with 2 % to 80 %, e.g. 5 % to 20 % by weight or 60 % to 80 % by weight, of a precipitated calcium sulfate component.
  • the weight proportion of said calcium sulfate component may be determined by any quantitative means that do not increase temperature too much, e.g. not higher than 45 °C, in order not to decompose the peroxygen component. Suitable means are, for instance, drying of a sample in an oven at 40 °C during 24 hours.
  • the hydrogen peroxide may be distributed onto or inside of the calcium sulfate particles, or the hydrogen peroxide may also, either completely or in part, be added (reaction of addition) to the calcium sulfate crystals in order to form a calcium sulfate perhydrate compound.
  • Individual calcium sulfate crystals according to any of the above embodiments of the invention preferably exhibit needle-shape. Particles are elongated or needle-shaped and are characterized, when measured through light microscopy, with an average needle length (i.e. average crystal length, based upon measurement of about 100 crystals) in the range of 1 ⁇ to 300 ⁇ , preferably in the range of 1 ⁇ to 150 ⁇ , more preferably 10 to 150 ⁇ .
  • the particle sizes vary from 0.1 ⁇ to 300 ⁇ , preferably from 0.1 ⁇ to 150 ⁇ .
  • these calcium sulfate particles may agglomerate into larger aggregates, e.g. aggregates of tens or hundreds of ⁇ to several mm.
  • particle size the average needle length when the particles are measured through light microscopy, or the average equivalent spherical diameter when they are measured through a laser diffraction method.
  • this invention relates to a method for producing a peroxygen release composition, comprising steps of: (a) reacting a water soluble calcium containing salt with sulfuric acid or a salt thereof in an aqueous hydrogen peroxide solution at a reaction temperature of 5 to 80 °C, preferably 15 to 40 °C, in a mixing apparatus with a rapid and intensive mixing into a white dispersion of calcium sulfate crystals,
  • said peroxygen release composition is dried to a dry product or powder by applying a suitable drying technique to said dispersion.
  • Said dry product may be further treated to obtain granules, said granules having an active oxygen content of about 5 % wt to about 20 % wt.
  • the viscous composition may be dried into the desired volume or shape.
  • the suitable dehydration or drying technique does not raise the product temperature above the range of 60 °C to 80 °C during drying.
  • a suitable additive such as a phosphonate may be added to the dispersion before drying.
  • the invention concerns a peroxygen release composition
  • a peroxygen release composition comprising a dispersion of calcium sulfate in an aqueous hydrogen peroxide solution, the calcium sulfate being formed in hydrogen peroxide and present as crystals in fibre, needle or sheet form with a particle size in the range of 1 ⁇ to 300 ⁇ when measured through light microscopy or in the range of 0.1 ⁇ to 300 ⁇ when measured through a laser diffraction method, the hydrogen peroxide being present in an amount comprised between 0.5 and 50 w %, the calcium sulfate being present in an amount comprised between 2.0 and 80.0 w %, and the composition having a viscosity of 200 cP to 20,000 cP, in the absence of additional thickening agent.
  • the calcium sulfate content is advantageously comprised between 2 and 20 w% of the composition.
  • calcium sulfate concentrations between 50 and 80 w% are advantageous, preferably 60 to 80 w %.
  • the peroxygen release composition of the present invention or produced by the present process unexpectedly can release a high percentage of the contained hydrogen peroxide immediately upon dispersion or dissolution in water at ambient room temperature or in cold water.
  • a stable, thickened dispersion of the peroxygen release compound can be produced in high concentrations without the need for stabilizing agents during the crystallization or precipitation process.
  • typical stabilizing agents such as phosphate-rich or complex organic molecules may thus be omitted, thereby avoiding the release of potentially harmful molecules to the environment.
  • said peroxygen release composition can be produced in high concentrations and can easily be separated from the original solvent, e.g. based on density difference by centrifugation.
  • the calcium sulfate crystals are preferably formed de novo by precipitation, by reacting dissolved calcium ions and sulfate ions in hydrogen peroxide solution. It has been found that when preformed commercial calcium sulfate is added to a hydrogen peroxide solution, the dispersion quickly becomes unstable and hydrogen peroxide starts to decompose. Moreover, preformed calcium sulfate at concentrations in the range of 2 wt % to 15 wt % did not result in sufficient viscosity increase of the composition in the range of 200 cP to 20,000 cP. When producing the calcium sulfate crystals within the hydrogen peroxide solution in accordance with the present invention, however, it is thus possible to obtain a stable and viscous peroxygen release composition.
  • either calcium or sulfate containing salts e.g. calcium chloride (CaCl 2 .2H 2 0) or sodium sulfate (Na 2 S0 4 ), or sulfuric acid
  • Said aqueous hydrogen peroxide solution may be a 1 to 70 % by weight solution.
  • Hydrogen peroxide solutions suitable for the present invention are technical grade hydrogen peroxide, e.g. a commercial 27.5 % hydrogen peroxide solution with a pH in the range of 1.5 - 4.0.
  • the hydrogen peroxide solution may be a food grade product.
  • the calcium sulfate may be present in an amount of 2 to 15 % wt. According to a more preferred embodiment, the calcium sulfate is present in an amount of 3 to 12 % wt, or even more preferably 4 to 10 % wt.
  • the molar ratio of calcium to sulfate may advantageously be comprised between 0.5 to 1 and 1 to 4.
  • the calcium sulfate used in the following illustrative embodiments can be efficiently produced at concentrations of about 25 to about 100 kilograms (CaS0 4 ) per m 3 of hydrogen peroxide solution, resulting in a dispersion of calcium sulfate in hydrogen peroxide.
  • Said dispersion, according to the present invention can be further thickened by a suitable concentration step, resulting in a viscous dispersion or paste with a final concentration of CaS0 4 in the range of about 100 to about 200 kilograms (CaS0 4 ) per m 3 of hydrogen peroxide solution.
  • No stabilizing agents need to be added to any of the above mentioned solutions in order to generate a stable viscous peroxygen release composition at the end.
  • the calcium sulfate crystals can be produced with a controllable size distribution in the hydrogen peroxide solution.
  • the size can be controlled by the control of the reaction time between the calcium and sulfate ions, e.g. a CaCl 2 .2H 2 0 solution and a Na 2 S0 4 solution in a hydrogen peroxide solution.
  • the calcium sulfate crystals have a tendency to grow longer.
  • the crystal length can be varied between micrometer to hundreds of micrometer by controlling the reaction time.
  • the calcium sulfate crystals formed according to the present invention increased from about 10 ⁇ after 1 minute of reaction time, to about 100 ⁇ after 60 minutes of reaction time, without stirring.
  • the crystal shape may change from fiber or wire-shaped to needle shaped and eventually sheets. Sheets may be composed of a combination of fibers, wires or needles into one crystal structure.
  • the size of the calcium sulfate crystals can be controlled by adjusting the temperature during the reaction between the calcium and sulfate ions in solution, e.g. the temperature of the solutions is increased to about 35 °C.
  • the size of the calcium sulfate crystals can be controlled by adding a suitable solvent, e.g. ethanol, to the calcium and sulfate containing salt solutions in hydrogen peroxide.
  • a suitable solvent e.g. ethanol
  • the composition additionally comprises an additive to control crystal growth selected from the following organic compounds: phosphonate, such as N,N,N',N'-ethylenediaminetetra (methylene phosphonic acid), N,N,N',N'-triethylenediaminetetra (methylene phosphonic acid), diethylenetriamine penta(methylene phosphonic acid), an acrylic- acid based polymer (polyacrylic acid), ethanol, or any combinations thereof.
  • phosphonate such as N,N,N',N'-ethylenediaminetetra (methylene phosphonic acid), N,N,N',N'-triethylenediaminetetra (methylene phosphonic acid), diethylenetriamine penta(methylene phosphonic acid), an acrylic- acid based polymer (polyacrylic acid), ethanol, or any combinations thereof.
  • calcium sulfate crystal growth may be stopped by addition of an organic compound such as a phosphonate compound or an acrylic-acid based polymer.
  • an organic compound such as a phosphonate compound or an acrylic-acid based polymer.
  • small calcium sulfate particles with good dispersive behavior result in little agglomeration.
  • Larger calcium sulfate particles result in higher viscosity of the peroxygen release composition, compared to smaller particles at the same concentration of CaS0 4 .
  • the size and shape of the calcium sulfate crystals according to the present invention are important characteristics of the peroxygen release composition.
  • the calcium sulfate crystals are characterized by a particle size in the range of 0.1 ⁇ to 150 ⁇ when measured through laser diffraction or in the range of 1 ⁇ to 150 ⁇ when measured through light microscopy
  • ions originating from a Ca 2+ and/or S0 4 2- " containing salt used for the production of the peroxygen release composition according to the present invention, such as for example chloride (e.g. originating from CaCl 2 .2H 2 0), nitrate (e.g. originating from Ca(N0 3 ) 2 ), sodium (e.g. originating from Na 2 S0 4 ) or potassium (e.g.
  • Peroxygen release compositions according to the current invention are found to be relatively stable over time, in the pH range of about 1.5 to about 8.5. Especially in the lower pH range, where hydrogen peroxide is mainly present in its undissociated form, hydrogen peroxide compositions are known to be more stable. Prior art compositions of persalts or compositions containing hydrogen peroxide are clearly unstable in the presence of metallic ions or other catalysts for hydrogen peroxide decomposition. The peroxygen release composition of the present invention or produced by the process of the present invention unexpectedly shows increased stability in the presence of metal ions.
  • the metal deactivation mechanism by the peroxygen release composition of the present invention works as follows: heavy metals adsorb on colloids of calcium sulfate or metal is encapsulated into calcium sulfate precipitates. The metallic compounds are thus rendered unavailable for reaction with hydrogen peroxide.
  • the high surface area and surface properties of the calcium sulfate component of the present invention may contribute to metal adsorption and further deactivation.
  • a concentrated, thickened dispersion of the peroxygen release composition for instance with a viscosity in the range of 5,000 - 20,000 cP, according to the present invention can be diluted with water, for example diluted 1 to 10 times, preferably 2 to 5 times, resulting in a stable dispersion with a decreased viscosity, e.g. in the range of 200 cP - 1,000 cP.
  • the diluted dispersion contains less % wt active oxygen, however still has sufficient viscosity to cling to non-horizontal surfaces or maintain small gas bubbles in a stable foam that does not readily collapse. These characteristics may make the product particularly interesting in cleaning or disinfection applications.
  • suitable additives may further be added to the composition, preferably selected from acetic or peracetic acid, iodophores, enzymes, surfactants, quaternary ammonium salts, benzalkonium chloride, benzoyl peroxide, persulfate, ethanol, and any combination thereof.
  • the peroxygen release composition according to the current invention is further dried to obtain a powder, granulate or dried composition with any shape of volume, such as tablets.
  • said composition is dewatered with a suitable drying technology into a composition containing:
  • a peroxygen release composition according to any of the above embodiments may release at least 40 % to 80 % of the activated oxygen present in said composition, e.g. 50 % to 70 % of the activated oxygen, within 30 seconds after dispersion of said composition into water.
  • the peroxygen release composition may be partially or entirely dissolved into the water.
  • the water solubility of the peroxygen release composition according to the present invention is at least 2 g/1 to about 100 g/1.
  • the limiting factor is the water solubility of the calcium sulfate component of said composition, being in the range of 2 - 2.5 g/1 in pure tap water at 20 °C.
  • peroxygen release composition comprising 2 % wt of calcium sulfate.
  • calcium sulfate solubility in water increases when temperature decreases, hence said peroxygen release composition is suitable for the quick release of hydrogen peroxide in cold water.
  • the invention relates to a method for producing a peroxygen release composition, comprising the steps of: (a) reacting a water soluble calcium containing salt with sulfuric acid or a salt thereof in an aqueous hydrogen peroxide solution at a reaction temperature of 5 to 80 °C in a mixing apparatus with a rapid and intensive mixing, advantageously at a rate comprised between 100 and 1000 rpm, into a white dispersion of calcium sulfate crystals;
  • the mixing step is continued until calcium sulfate particles are formed having attained a suitable size in the range of 1 ⁇ - 300 ⁇ when measured through light microscopy, or in the range of 0.1 ⁇ - 300 ⁇ when measured through a laser diffraction method.
  • the reaction temperature is advantageously between 15 °C and 40 °C.
  • the reaction may be designed as a batch crystallization process, as a continuous crystallization process, as a once-through flow system, or other suitable process designs.
  • the water soluble Ca salt may be either added to the reaction as a solid, as a concentrated solution in water or as a concentrated aqueous hydrogen peroxide solution.
  • Suitable calcium salts are e.g. calcium chloride or calcium nitrate.
  • the S0 4 " salt may be either added to the reaction as a solid or as a concentrated aqueous hydrogen peroxide solution, in order to have the final solution as concentrated as possible.
  • Suitable sulfate salts are e.g. sodium sulfate, sodium bisulfate or potassium sulfate.
  • a crystallization process control agent may be added during the reaction in the mixing apparatus, selected from the following organic compounds: phosphonate, such as N,N,N',N'-ethylenediaminetetra (methylene phosphonic acid), ⁇ , ⁇ , ⁇ ', ⁇ '- triethylenediaminetetra (methylene phosphonic acid), diethylenetriamine penta(methylene phosphonic acid), an acrylic-acid based polymer (polyacrylic acid), ethanol, or any combinations thereof.
  • phosphonate such as N,N,N',N'-ethylenediaminetetra (methylene phosphonic acid), ⁇ , ⁇ , ⁇ ', ⁇ '- triethylenediaminetetra (methylene phosphonic acid), diethylenetriamine penta(methylene phosphonic acid), an acrylic-acid based polymer (polyacrylic acid), ethanol, or any combinations thereof.
  • a crystallization process control agent may further be added after the thickening step, to the viscous dispersion or paste, selected from the following organic compounds: phosphonate, such as N,N,N',N'-ethylenediaminetetra (methylene phosphonic acid), N,N,N',N'-triethylenediaminetetra (methylene phosphonic acid), diethylenetriamine penta(methylene phosphonic acid), an acrylic- acid based polymer (polyacrylic acid), ethanol, or any combinations thereof.
  • organic compounds such as N,N,N',N'-ethylenediaminetetra (methylene phosphonic acid), N,N,N',N'-triethylenediaminetetra (methylene phosphonic acid), diethylenetriamine penta(methylene phosphonic acid), an acrylic- acid based polymer (polyacrylic acid), ethanol, or any combinations thereof.
  • thickening of the dispersion is achieved by disc centrifugation, decanter centrifuge or filtration.
  • said peroxygen release composition is dried to a dry product or powder by applying a suitable drying technique to said dispersion, such as spray drying, fluidized bed drying, evaporation, vacuum drying, drying by air, belt drying, drying in a rotating drum, or any other suitable technique to remove moisture.
  • a suitable drying technique such as spray drying, fluidized bed drying, evaporation, vacuum drying, drying by air, belt drying, drying in a rotating drum, or any other suitable technique to remove moisture.
  • the drying may be applied directly to the said dispersion or to the thickened dispersion, obtained by a suitable concentration technique.
  • said dry product may be further treated by compacting to shells, breaking and screening the shells, dry granulating the broken and screened material to obtain a granulate, said granulate having an activated oxygen content of about 5 % wt to about 20 % wt.
  • the viscous composition may be dried to any other solid form of any shape or volume, such as produced by cutting, breaking, compacting or molding the viscous composition into the desired shape before drying.
  • the suitable dehydration or drying technique does not increase the product temperature above the range of 60 °C to 80 °C during drying.
  • a suitable additive such as a phosphonate may be added to the dispersion before drying, e.g. to the concentrated sediment obtained by centrifugation of the dispersion, in a concentration of 1 % wt to 5 % wt, preferably 1 % wt to 3 % wt.
  • the peroxygen release composition of the invention may be used in liquid or solid oxygen bleaches for applications in the fields of detergents, laundry, paper & pulp.
  • composition according to the present invention is further suitable for use in disinfectants, cleaning agents, pharmaceutical, textile and industrial applications and in various personal care applications such as hair and tooth whitening.
  • the viscosity and bright white color of the thickened dispersion make the composition very compatible with commercial liquid bleach formulations and sanitizing or disinfecting formulations suitable for foam spraying or other means of application on non- horizontal surfaces.
  • the composition may also be suitable for use in wound care or wound dressing bandages.
  • the concentration of active oxygen in the thickened dispersion was determined either by an adaptation from the method described by Schumb et al (1955), a method based on a titrimetric measurement based on permanganate titration in an acid environment, or by dilution in water and measure with peroxide colorimetric dipsticks reagent strips (Merck). The dispersion was found to contain 25 % wt to 30 % wt of active oxygen.
  • the dry weight of the white composition was determined by drying during 24 h in an oven at 40 °C.
  • the % DM (Dry Matter) was determined to be approx. 20 - 22 %. A large portion of the dry weight could be attributed to calcium sulfate.
  • the composition was found to be stable over time. After 2 months of storage at ambient temperature, the active oxygen content was found to be 22 % wt - 25 % wt. The viscosity of the composition was in the range of 10,000 cP.
  • a 50 g aliquot of the composition was further diluted 5 times with tap water, and resulted in a stable dispersion of approx. 5 % wt active oxygen. After 1 month, the sample still contained approx. the same concentration of active oxygen. The viscosity was about 500 cP.
  • EXAMPLE II The composition obtained from Example I was distributed over 50 g aliquots. To each aliquot, the pH was changed by addition of HC1 and NaOH and stability of the composition over a broad pH range was studied.
  • the crystals After 2 hours, the crystals had reached an average length of about 150 ⁇ , estimated by microscopic comparison to a graduated tick mark. Agglomeration may have occurred at this stage. The crystals were needle shaped, and some sheet structures were observed. To remove the excess of liquid, the dispersion was put over a filter paper with a pore size of maximum 5 ⁇ , and allowed to concentrate overnight. A total of 350 g thickened dispersion at pH 3 was obtained. The concentration of active oxygen in the Sample was in the range of 5 % - 7 %. The viscosity of the composition was in the range of 5,000 cP. The composition was stable in time. EXAMPLE IV.
  • ferric EDTA was added to 3.5 grams of a 27.5 % wt H2O2 solution.
  • composition 50 ppm 50 ppm 45 ppm
  • EXAMPLE I In this example, the stabilizing effect of the composition according to EXAMPLE I in the presence of Fe-catalyst is observed, compared to a regular hydrogen peroxide solution.
  • Example II The composition obtained from Example I after centrifugation was mixed with 3 % wt of diethylenetriamine penta(methylene phosphonic acid) and dried in an air flow at approx. 25 °C.
  • the resulting dry product could be ground into a fine powder and was found to be composed of approx. 15 % wt to 20 % wt of hydrogen peroxide. At least 80 % of the contained hydrogen peroxide was released within 30 seconds when 1 gram of the powder was dissolved in 500 mL of cold tap water.
  • EXAMPLE VI 82 g CaCl 2 .2H 2 0 solubilized in 0.5 L H 2 0 2 (27%) was added to 85 g Na 2 S0 4 solubilized in 0.5 L H 2 0 2 (27 %). The resulting mixture was stirred and diethylenetriamine penta(methylene phosphonic acid) was added. The liquid was filtered and 400 grams of thick white paste containing approx. 19 % hydrogen peroxide was obtained. The pH of the product was 2.5.
  • the paste was heated to 80 °C for 16 hours and the product was found to be heat stable, since the hydrogen peroxide content remained constant.
  • the dry weight after filtration was determined to be 29.6 %. This DW% was determined by placing a sample at 105 °C for 24 h and measuring the weight difference.
  • EXAMPLE VIII Viscosity data.
  • the dynamic viscosity of the product obtained from EXAMPLE VI was determined with a Brookfield DVII+Pro viscometer at different spindle rotation speeds. During the dynamic viscosity measurements, the rotations per minute (rpm) were gradually increased, starting at 10 rpm, increasing to 50 rpm up to a final spindle speed of 100 rpm. The RV7 spindle was used for these measurements. The measurements were done at 20 °C. The data are summarized in the table 5.
  • Samples from the product obtained from the above Examples were analyzed by means of a laser granulometer type Malvern Mastersizer 2000 in humid phase. 3 grams of sample were added to 50 mL water under magnetic stirring. After 10 minutes of stirring, a small portion of the sample was taken and added to the measuring cell of the apparatus, in order to obtain an obscuration percentage of 10 %. Afterwards, the sample was left under agitation (2800 rpm) in the measuring cell during 5 minutes and the measurement was repeated. This time delay of 5 minutes allowed to observe the effect of agitation time on the particle size.
  • the percentiles D(0.1), D(0.5) and D(0.9) are the values below which, respectively, 10 percent, 50 percent and 90 percent of the observations were found.
  • the span is a distribution width parameter and is calculated by using the formula: [d(0.9)-d(0.1)] / d(0.5).
  • the mode is the peak of the frequency distribution.

Abstract

L'invention porte sur des compositions contenant un composé peroxygéné stabilisées, à la fois sous forme visqueuse épaissie et sous forme sèche. Les compositions contiennent des cristaux de sulfate de calcium nouvellement synthétisés qui servent d'épaississant et d'agent stabilisant vis-à-vis d'une décomposition catalysée par un métal. Plus précisément, l'invention porte sur une composition comprenant 0,5 % en poids à 50 % en poids de peroxyde d'hydrogène, 2,0 % en poids à 80,0 % en poids de cristaux de sulfate de calcium nouvellement synthétisés, lesquels ont chacun une forme lamellaire ou aciculaire, et de l'eau, ladite composition ayant une viscosité de 200 cP à 20 000 cP. L'invention porte en outre sur un procédé pour la fabrication de la composition, comprenant la réaction d'un sel contenant du calcium hydrosoluble avec de l'acide sulfurique ou un sel de celui-ci dans une solution aqueuse de peroxyde d'hydrogène à une température de réaction allant jusqu'à 80°C dans un appareil de mélange, suivie d'une étape de concentration afin d'épaissir en une dispersion visqueuse ou pâte stable contenant au moins 2 % en poids et de préférence 10 % en poids à 15 % en poids de CaSO4. Les compositions sont appropriées pour être utilisées comme désinfectants, comme agents nettoyants et dans un grand nombre d'applications d'hygiène personnelle, pharmaceutiques, de blanchiment de textile et industrielles.
PCT/EP2013/059824 2012-05-11 2013-05-13 Compositions libérant un composé peroxygéné et leur procédé de production WO2013167752A1 (fr)

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IN9212DEN2014 IN2014DN09212A (fr) 2012-05-11 2013-05-13
EP13722417.6A EP2847128A1 (fr) 2012-05-11 2013-05-13 Compositions libérant un composé peroxygéné et leur procédé de production
CN201380024576.5A CN104364190A (zh) 2012-05-11 2013-05-13 过氧释放组合物及其制造方法
US14/399,842 US20150086647A1 (en) 2012-05-11 2013-05-13 Peroxygen release compositions and method for producing them
BR112014028049A BR112014028049A2 (pt) 2012-05-11 2013-05-13 composições de liberação de peroxigênio e método para a produção das mesmas
RU2014150001A RU2014150001A (ru) 2012-05-11 2013-05-13 Композиции, высвобождающие пероксид водорода, и способ их получения

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EP12167726.4A EP2662329A1 (fr) 2012-05-11 2012-05-11 Compositions à libération de peroxygène et leur procédé de production

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CN104906616B (zh) * 2015-05-09 2017-08-18 安徽科技学院 一种环保型除臭剂的制备方法
WO2017069820A2 (fr) 2015-07-17 2017-04-27 Next Science, Llc Composition antimicrobienne efficace contre les endospores
CA3033937A1 (fr) 2016-08-30 2018-03-08 Church & Dwight Co., Inc. Composition et procede de desactivation d'allergenes
CN109843807B (zh) * 2016-10-17 2021-12-14 林德公司 用于生产具有独特的性质的硫酸钙半水合物的新方法
CN112080927A (zh) * 2019-06-13 2020-12-15 青岛奥洛思新材料有限公司 用于麻纤维煮漂工艺的氧漂助剂及其制备方法
CN111962285A (zh) * 2020-08-04 2020-11-20 天津工业大学 一种牦牛绒的漂白剂及处理方法
CN114875654B (zh) * 2022-06-10 2023-11-21 山东中康国创先进印染技术研究院有限公司 一种棉织物退煮漂低强损冷轧堆前处理工艺
CN115465932A (zh) * 2022-10-24 2022-12-13 中化学朗正环保科技有限公司 一种去除钙盐浓缩液中硫酸根离子的方法

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US20150086647A1 (en) 2015-03-26
RU2014150001A (ru) 2016-07-10
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